Cathodically coloring yellow soluble electrochromic and light emitting polymers

ABSTRACT

Embodiments of the invention are directed to yellow-to-transmissive conjugated polymers, a method to prepare the yellow conjugated polymers, the use of the yellow conjugated polymers in an electrochromic and/or electroluminescent device comprising neutral state primary subtractive colored conjugated polymers, and a method to prepare the device comprising the yellow conjugated polymer. The yellow conjugated polymers comprise a sequence of dioxythiophene units alternating with aromatic units, thiophene units, furan units, and/or pyrrole units. The yellow conjugated polymers are prepared by cross-condensation reactions. The yellow conjugated polymers can be soluble and preparation of the device involves deposition of the yellow conjugated polymer from solution onto a surface.

CROSS-REFERENCE TO RELATED APPLICATION

The present application claims the benefit of U.S. ProvisionalApplication Ser. No. 61/407,615, filed Oct. 28, 2010, which is herebyincorporated by reference herein in its entirety, including any figures,tables, or drawings.

The subject invention was made with government support under the AirForce Office of Scientific Research, Contract No. FA9550-09-1-0320. Thegovernment has certain rights to this invention.

BACKGROUND OF INVENTION

Non-emissive display technologies using electrochromic (EC) materialsare of interest for devices with the ability to be viewed in a widevariety of lighting conditions, and for large area devices that can befabricated using convenient inexpensive printing techniques. ECmaterials that can display three primary colors could be used to createfull color display devices where the expression of any color can beachieved through the control of the intensity of each of the primarycolors. Such devices require colors that can be switched “on” or “off”rapidly. Cathodically-coloring conjugated polymers are a class ofmaterials that can demonstrate this rapid switching and polymers havebeen made that strongly absorb light in the visible region of thespectrum in a neutral state and upon oxidation absorb almost exclusivelyNIR radiation, leaving a near colorless, highly transmissive oxidizedstate. The addition of the colors red, green, and blue has been exploredfor displays from conjugated polymers; however, for truly non-emissivedisplays a primary subtractive color set, red, yellow and blue (RYB) orcyan, magenta and yellow (CMY), must be employed to produce all colors.Kobayashi et al., Solar Energy Materials and Solar Cells, 2008, 92,136-9 has demonstrated a display from primary subtractive coloredmolecular electrochromic species, but the color system requires a veryhigh potential (−2 V vs. Ag/AgCl) for switching and requires more thanten seconds and the sub-second switching speeds needed for deviceapplications is not possible. Additionally, some colors are not stableto repeated switching.

The lack of yellow cathodically coloring conjugated polymers with bandgaps of about 2.3 to about 2.8 eV has limited the development ofmulticolor display prototypes using primary subtractive coloredconjugated polymers. The high band gap required to achieve a yellowcolor has prohibited switching from visible absorption bands in theneutral state to a transmissive NIR absorbing state upon oxidation. Afew anodically coloring yellow conjugated polymers have been produced,Liou et al., Macromolecules, 2008, 42, 125-34 and Wang et al., PolymerChemistry, 2010, 1, 1013-23. Although, in principle these conjugatedpolymers can be incorporated into display devices, in practice veryspecific potentials are required to achieve a yellow color without abrownish hue and these anodically coloring conjugated polymers have notdisplayed the potential for long term stability. The best electrochromicmaterial that displays a yellow color consists of a conjugated oligomercontaining pendant acrylate groups that can be synthesized and patternedby a UV mediated process, Nielsen et al., Journal of the AmericanChemical Society, 2008, 130, 9734-46. The conjugated oligomer segmentsof the polyacrylate switch from a yellow neutral state to an intenseblue cation radical state and ultimately a less intense but stillstrongly blue dicationic state.

A yellow to transmissive cathodically coloring conjugated polymer isvery desirable as it is the only color missing from the primarysubtractive colored conjugated polymers. A non-emissive conjugatedpolymer display having a primary subtractive color set can be producedwith a yellow to transmissive cathodically coloring conjugated polymer.

BRIEF SUMMARY

Embodiments of the invention are directed to conjugated polymers havinga fully conjugated polymeric sequence of at least two alternating triadsof a first and second repeating unit. The first repeating units aredioxyheterocyclic units selected from one or more of dioxythiophene,dioxyfuran, dioxypyrrole, or dioxyselenophene or any combinationthereof. The second repeating units are selected from aromatic,thiophene, furan, pyrrole, selenophene or any combination thereof. Theconjugated polymer is yellow in its neutral state and displays anabsorption maximum between 300 and 500 nm and upon oxidation istransmissive between 400-750 nm. The fully conjugated polymeric sequencecan be a polymer having alternating first and second repeating units, analternating copolymer, an ABA copolymer, or it can be a portion of arandom copolymer where statistically at least two alternating triads areformed. The fully conjugated polymeric sequence can be a portion ofnetwork or of a block, graft, branched, hyperbranched, or dendriticcopolymer.

In an embodiment of the invention, the yellow conjugated polymer or apolymeric precursor of the conjugated polymer can be soluble in at leastone solvent, which permits deposition of a film of the polymer fromsolution. In one embodiment, a thin film comprising the conjugatedpolymer in the neutral state can display a transmittance of less thanabout 40% between 400 nm and 500 nm and greater than about 90%transmittance from 600 nm-750 nm, and can undergo oxidation to atransmissive state having a transmittance of more than about 70% between400 and 750 nm. The yellow conjugated polymer can be electrochromicand/or electroluminescent.

Another embodiment of the invention is directed to the preparation ofthe yellow conjugated polymer by cross-coupling nucleophilic monomericunits with electrophilic monomeric units to yield the conjugated polymeror a precursor of the conjugated polymer. Cross-coupling can be a Stillecoupling, Kumada coupling, Hiyama coupling, Negishi coupling, Suzukicoupling, or Grignard methathesis (GRIM).

Other embodiments of the invention are directed to electrochromic,electroluminescent, and/or combined electrochromic, electroluminescentdevices comprising the yellow conjugated polymer. When combined withother electrochromic polymers (conjugated polymers) having other primarysubtractive colors in a neutral state and are transmissive in anoxidized state a full color device can be achieved.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows various aromatic and heterocyclic repeating units that canbe the second repeating unit of an alternating sequence of the yellowconjugated polymer according to an embodiment of the invention.

FIG. 2 shows a reaction scheme for the preparation of exemplary yellowconjugated polymers, ECP Yellow-1 and ECP Yellow-2, by a Suzukicondensation, according to an embodiment of the invention.

FIG. 3 shows the spectroelectrochemical analysis of ECP Yellow-1,according to an embodiment of the invention, where the polymersabsorption spectra (top) and % transmittance spectra (bottom) areplotted for various applied voltages from 180 mV to 1080 mV vs. Fc/Fc⁺at 50 mV steps.

FIG. 4 shows the color change as L*a*b* values for ECP Yellow-1,according to an embodiment of the invention, where a*b* values areplotted as a function of electrochemical doping level for 50 mV steps.

FIG. 5 shows potential square wave absorptometry plots for ECP Yellow-1,according to an embodiment of the invention, that measured at 455 nm,180 to 1080 mV vs. Fc/Fc+ in 0.2 M Li BTI/PC solution, Pt wire CE wherethe switch time was increased from 10 s step for 40 s (2 cycles), 2 sstep for 20 s (5 cycles), 1 s step for 30 s (15 cycles), 0.5 s step for20 s (20 cycles), and 0.25 s step for 20 s (40 cycles).

FIG. 6 shows a normalized electroluminescence spectrum for ECP Yellow-1,according to an embodiment of the invention, with an applied currentdensity of 300 mA/cm².

FIG. 7 (top) shows thin films deposited on transparent substrates andpositioned as a Venn diagram of an exemplary yellow conjugated polymer,ECP Yellow-1, a blue conjugated polymer, and red conjugated polymer,where two overlapping films display the secondary colors green, orange,and purple, and where three overlapping films display black and thedemonstration (bottom) of the films switching from their neutral coloredstates (left) to highly transmissive states (right) upon oxidation.

FIG. 8 shows the spectroelectrochemical analysis of ECP Yellow-2,according to an embodiment of the invention, where the polymersabsorption spectra (top) and % transmittance spectra (bottom) areplotted for various applied voltages from 180 mV to 1080 mV vs. Fc/Fc⁺at 50 mV steps.

FIG. 9 shows the color change as L*a*b* values for ECP Yellow-2,according to an embodiment of the invention, where a*b* values areplotted as a function of electrochemical doping level for 50 mV steps.

FIG. 10 shows potential square wave absorptometry plots for ECPYellow-2, according to an embodiment of the invention, that measured at434 nm, 180 to 1080 mV vs. Fc/Fc+ in 0.2 M Li BTI/PC solution, Pt wireCE where the switch time was increased from 10 s step for 100 s (5cycles), 5 s step for 50 s (5 cycles), 2 s step for 40 s (10 cycles), 1s step for 40 s (20 cycles), 0.5 s step for 20 s (20 cycles), and 0.25 sstep for 10 s (20 cycles).

DETAILED DISCLOSURE

Embodiments of the invention are directed to yellow-to-transmissiveswitching cathodically coloring conjugated polymers, their preparationand displays having a palette of primary subtractive colors preparedwith these neutral state yellow conjugated polymers. The yellowconjugated polymers exhibit high optical contrasts at the wavelength ofpeak absorption in the neutral state, which upon oxidation become highlytransmissive throughout the entire visible region. For purposes of theinvention, high transmissivity of a conjugated polymer is considered tobe achieved when a film can be switched from transmittance less than 40%between 400 nm and 500 nm with transmittance greater than 90% from 600nm-750 nm, to a film which displays greater than 70% transmittancebetween 400 nm and 750 nm. In embodiments of the invention, the yellowconjugated polymer is soluble in at least one solvent, for exampletoluene, chloroform, dichloromethane, hexanes, tetrahydrofuran,chlorobenzene, water, ethanol, other solvents or combination ofsolvents. From solution, the soluble yellow conjugated polymer isreadily incorporated into an electrochromic device using convenientdeposition methods such as spin coating, spray casting, and printingtechniques such as screen printing, inkjet printing, offset printing,rotogravure, slot-dye coating, or flexography to form a thin film. Inembodiments of the invention, yellow-to-transmissive conjugated polymerscan be included in either reflective or transmissive ECDs which useconjugated polymers of three primary colors, either red, yellow and blue(RYB) or cyan, magenta and yellow (CMY), in a complete subtractive colorspace to allow any color to be produced by the appropriate colorcombination. These complete multicolor conjugated polymer devices can beused in various display technologies such as displays for electronics,full color e-books, and signage. In other embodiments of the invention,electroluminescent or combination electroluminescent/electrochromicdevices are formed, having light emitting and/or electrochromicproperties.

In an embodiment of the invention, the yellow conjugated polymers aretransmissive and color neutral in the oxidized state and yellow in aneutral state with peak absorption, λ_(max), at about 450 nm, where as athin film, the yellow conjugated polymers display less than 20%transmission between 400 and 500 nm and having an onset of absorption of2.3-3.0 eV in the neutral state and can be converted by electrochemicalreaction to a film with greater than 70% transmission throughout thevisible spectrum from 400-750 nm. The yellow conjugated polymers displayhigh optical contrast in the visible region and possess rapid switchingspeeds and stability upon repetitive switching. The yellow conjugatedpolymers can be processed from solution, which is advantageous for usein reflective and transmissive electrochromic devices (ECDs),electroluminescent devices, or combinationelectroluminescent/electrochromic devices.

Embodiments of the invention are directed to yellow conjugated polymersthat comprise portions of a polymer that have a fully conjugated polymersequence of alternating repeating units where a first repeating unit isa dioxyheterocyclic unit that alternates with a second repeating unitthat is a substituted or unsubstituted aromatic unit or heterocyclicunit other than a dioxysubstituted heterocyclic unit. Thedioxyheterocyclic units can be 3,4-alkylenedioxythiophenes,3,4-alkylenedioxyselenophenes, 3,4-alkylenedioxypyrroles,3,4-alkylenedioxyfurans, which are substituted on the alkylene bridge,3,4-dialkoxythiophenes, 3,4-dialkoxyselenophenes, 3,4-dialkoxypyrroles,3,4-dialkoxyfurans, or any combination thereof, where pyrrole rings areeither unsubstituted or substituted, for example, with alkyl groups andalkyl groups that are further substituted. Aromatic units can beunsubstituted or substituted with alkyl groups that may be furthersubstituted in any manner that does not change the conjugation of thebase group or introduce an additional colored moiety, for example thefurther substitution can include but is not limited to: alkene, alkyne,ether, ester, amide, carboxylic acid, sulfonate, or amine functionalizedchains. The alkyl groups can be linear, branched, or cyclic instructure. Of the second repeating units, aromatic units include, butare not limited to, 1,4-phenylenes, biphenylenes, fullerenes,naphthalenes, anthracenes, or combinations thereof. Some exemplaryaromatic units are included in FIG. 1. The R groups, for the structuresshown in FIG. 1, can be, independently, H, C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl,C₂-C₃₀ alkynyl, C₆-C₁₄ aryl, C₇-C₃₀ arylalkyl, C₈-C₃₀ arylalkenyl,C₈-C₃₀ arylalkynyl, hydroxy, C₁-C₃₀ alkoxy, C₆-C₁₄ aryloxy, C₇-C₃₀arylalkyloxy, C₂-C₃₀ alkenyloxy, C₂-C₃₀ alkynyloxy, C₈-C₃₀arylalkenyloxy, C₈-C₃₀ arylalkynyloxy, CO₂H, C₂-C₃₀ alkylester, C₇-C₁₅arylester, C₈-C₃₀ alkylarylester, C₃-C₃₀ alkenylester, C₃-C₃₀alkynylester, NH₂, C₁-C₃₀ alkylamino, C₆-C₁₄ arylamino, C₇-C₃₀(arylalkyl)amino, C₂-C₃₀ alkenylamino, C₂-C₃₀ alkynylamino, C₈-C₃₀(arylalkenyl)amino, C₈-C₃₀ (arylalkynyl)amino, C₂-C₃₀ dialkylamino,C₁₂-C₂₈ diarylamino, C₄-C₃₀ dialkenylamino, C₄-C₃₀ dialkynylamino,C₇-C₃₀ aryl(alkyl)amino, C₇-C₃₀ di(arylalkyl)amino, C₈-C₃₀alkyl(arylalkyl)amino, C₁₅-C₃₀ aryl(arylalkyl)amino, C₈-C₃₀alkenyl(aryl)amino, C₈-C₃₀ alkynyl(aryl)amino, C(O)NH₂ (amido), C₂-C₃₀alkylamido, C₇-C₁₄ arylamido, C₈-C₃₀ (arylalkyl)amido, C₂-C₃₀dialkylamido, C₃₂-C₂₈ diarylamido, C₈-C₃₀ aryl(alkyl)amido, C₁₅-C₃₀di(arylalkyl)amido, C₉-C₃₀ alkyl(arylalkyl)amido, C₁₆-C₃₀aryl(arylalkyl)amido, thiol, C₁-C₃₀ hydroxyalkyl, C₆-C₁₄ hydroxyaryl,C₇-C₃₀ hydroxyarylalkyl, C₃-C₃₀ hydroxyalkenyl, C₃-C₃₀ hydroxyalkynyl,C₈-C₃₀ hydroxyarylalkenyl, C₈-C₃₀ hydroxyarylalkynyl, C₃-C₃₀ polyether,C₃-C₃₀ polyetherester, C₃-C₃₀ polyester C₃-C₃₀ polyamino, C₃-C₃₀polyaminoamido, C₃-C₃₀ polyaminoether, C₃-C₃₀ polyaminoester, C₃-C₃₀polyamidoester, C₃-C₃₀alkylsulfonic acid, C₃-C₃₀alkylsulfonate salt,C₁-C₃₀ carboxy late salt, thiocarboxylate salt, dithiocarboxylate saltor C₃-C₃₀alkylC₁-C₄ trialkyammonium salt. The R′ groups, in therepeating units of FIG. 1, can be, independently, H, C₁-C₃₀ alkyl,C₂-C₃₀ alkenyl, C₂-C₃₀ alkynyl, C₆-C₁₄ aryl, C₇-C₃₀ arylalkyl, C₈-C₃₀arylalkenyl, C₈-C₃₀ arylalkynyl, C₁-C₃₀ hydroxyalkyl, C₆-C₁₄hydroxyaryl, C₇-C₃₀ hydroxyarylalkyl, C₃-C₃₀ hydroxyalkenyl, C₃-C₃₀hydroxyalkynyl, C₈-C₃₀ hydroxyarylalkenyl, C₈-C₃₀ hydroxyarylalkynyl,C₃-C₃₀ polyether, C₃-C₃₀ polyetherester, C₃-C₃₀ polyester C₃-C₃₀polyamino, C₃-C₃₀ polyaminoamido, C₃-C₃₀ polyaminoether, C₃-C₃₀polyaminoester, C₃-C₃₀ polyamidoester, C₃-C₃₀alkylsulfonic acid,C₃-C₃₀alkylsulfonate salt, C₁-C₃₀ alkylcarboxylate salt, C₁-C₃₀alkylthiocarboxylate salt, C₁-C₃₀ alkyldithiocarboxylate salt or C₃-C₃₀alkyl C₁-C₄ trialkyammonium salt. The R″ groups, in the repeating unitsof FIG. 1, can be, independently, H, C₁-C₃₀ alkyl, C₃-C₃₀ alkenyl,C₂-C₃₀ alkynyl, C₆-C₁₄ aryl, C₇-C₃₀ arylalkyl, C₈-C₃₀ arylalkenyl,C₈-C₃₀ arylalkynyl. The R″ groups that are not H have sp³ hybridizedcarbons attached to the heterocyclic ring. Alkyl groups can be straight,branched, multiply branched, cyclic, or polycyclic where cyclic andpolycyclics can be unsubstituted, substituted, or polysubstituted,alkenyl can be a monoene, conjugated or non-conjugated polyene,straight, branched, multiply branched, cyclic, or polycyclic, terminalor internal, substituted at any carbon, E or Z isomers or mixturethereof, alkynes can be mono-yne, conjugated or non-conjugated poly-yne,terminal or internal, substituted at any carbon, aryl groups can becyclic, fused or unfused polycyclic of any geometry, asymmetricfunctional groups, such as ester and amido, can have either orientationwith respect to the alkylenedioxythiophene rings, poly can be 2 or more.Heteroatoms in substituents R¹-R⁸ can be at any position of thosesubstituents. For example an oxygen of an ether or ester or a nitrogenof an amine or amide can be in the alpha, beta, gamma or any otherposition relative to the point of attachment to the aromatic groups.Heteroatom containing substituents can have a plurality of heteroatoms,for example ether can be a monoether, a diether or a polyether, aminecan be a monoamine, a diamine or a polyamine, ester can be a monoester,a diester, or a polyester, and amide can be a monoamide, a diamide or apolyamide. Ethers and esters groups can be thioethers, thioesters andhydroxy groups can be thiol (mercapto) groups, where sulfur issubstituted for oxygen. Salts can be those of alkali or alkali earthmetals, ammonium salts, or phosphonium salts.

In some embodiments of the invention, the alternating polymeric sequencecan be a polymer, such as that shown in FIG. 2, which can be viewed as acondensation homopolymer of two complementary monomers. Copolymers canbe made where first repeating units can include a plurality of differentdioxyheterocyclic units and the second repeating units can include aplurality of different aromatic or heterocyclic units. As can beappreciated by those skilled in the art, a linear polymeric sequence ofthis type is readily formed by the condensation of appropriatelysubstituted difunctional monomers where the different alternating unitsare from monomers with complementary reactive functionality. The use ofmonofunctional and/or trifunctional monomers of one or more of thealternating units allows the control of the molecular weight, branching,hyperbranching, and network formation of the yellow conjugated polymers,and one or more repeating unit can be appropriately substituted to bemonofunctional toward formation of the alternating sequence and allowformation of various different kinds of block copolymers simultaneouslyor sequentially where the block copolymer contains a yellow conjugatedpolymer block.

In embodiments of the invention, the yellow conjugated polymer can be arandom copolymer of three or more repeating units where the polymer hasa sequence of at least two alternating triads (series of three repeatingunits) that can be either a first unit-second unit-first unit triad or asecond unit-first unit-second unit triad. The additional repeating unitsmay increase the conjugation beyond the triad or may be a repeating unitthat does not increase the conjugation length beyond the triad. As canbe appreciated by those skilled in the art, to permit formation of afilm that has sufficient color intensity, the use of a thin filmrequires a greater proportion of the yellow conjugated polymer portionshaving the alternating triads than does a thicker film.

In embodiments of the invention, a yellow conjugated polymer has thealternating first and second repeating unit sequence of the structure:

where: A is an aromatic unit, thiophene unit, furan unit, pyrrole unit,selenophene, or any combination thereof; n is 2 to 200,000; x is 0 or 1;y is 0 or 1; X is S, Se, O, or NR; R is H, C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl,C₂-C₃₀ alkynyl, C₆-C₁₄ aryl, C₇-C₃₀ arylalkyl, C₈-C₃₀ arylalkenyl,C₈-C₃₀ arylalkynyl, C₁-C₃₀ hydroxyalkyl, C₆-C₁₄ hydroxyaryl, C₇-C₃₀hydroxyarylalkyl, C₃-C₃₀ hydroxyalkenyl, C₃-C₃₀ hydroxyalkynyl, C₈-C₃₀hydroxyarylalkenyl, C₈-C₃₀ hydroxyarylalkynyl, C₃-C₃₀ polyether, C₃-C₃₀polyetherester, C₃-C₃₀ polyester C₃-C₃₀ polyamino, C₃-C₃₀polyaminoamido, C₃-C₃₀ polyaminoether, C₃-C₃₀ polyaminoester, C₃-C₃₀polyamidoester C₃-C₃₀alkylsulfonic acid, C₃-C₃₀alkylsulfonate salt,C₁-C₃₀ alkylcarboxylate salt, C₁-C₃₀ alkylthiocarboxylate salt, C₁-C₃₀alkyldithiocarboxylate salt or C₃-C₃₀ alkyl C₁-C₄ trialkyammonium salt;and R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are independently H, C₁-C₃₀ alkyl,C₂-C₃₀ alkenyl, C₂-C₃₀ alkynyl, C₆-C₁₄ aryl, C₇-C₃₀ arylalkyl, C₈-C₃₀arylalkenyl, C₈-C₃₀ arylalkynyl, hydroxy, C₁-C₃₀ alkoxy, C₆-C₁₄ aryloxy,C₇-C₃₀ arylalkyloxy, C₂-C₃₀ alkenyloxy, C₂-C₃₀ alkynyloxy, C₈-C₃₀arylalkenyloxy, C₈-C₃₀ arylalkynyloxy, CO₂H, C₂-C₃₀ alkylester, C₇-C₁₅arylester, C₈-C₃₀ alkylarylester, C₃-C₃₀ alkenylester, C₃-C₃₀alkynylester, NH₂, C₁-C₃₀ alkylamino, C₆-C₁₄ arylamino, C₇-C₃₀(arylalkyl)amino, C₂-C₃₀ alkenylamino, C₂-C₃₀ alkynylamino, C₈-C₃₀(arylalkenyl)amino, C₈-C₃₀ (arylalkynyl)amino, C₂-C₃₀ dialkylamino,C₁₂-C₂₈ diarylamino, C₄-C₃₀ dialkenylamino, C₄-C₃₀ dialkynylamino,C₇-C₃₀ aryl(alkyl)amino, C₇-C₃₀ di(arylalkyl)amino, C₈-C₃₀alkyl(arylalkyl)amino, C₁₅-C₃₀ aryl(arylalkyl)amino, C₈-C₃₀alkenyl(aryl)amino, C₈-C₃₀ alkynyl(aryl)amino, C(O)NH₂ (amido), C₂-C₃₀alkylamido, C₇-C₁₄ arylamido, C₈-C₃₀ (arylalkyl)amido, C₂-C₃₀dialkylamido, C₁₂-C₂₈ diarylamido, C₈-C₃₀ aryl(alkyl)amido, C₁₅-C₃₀di(arylalkyl)amido, C₉-C₃₀ alkyl(arylalkyl)amido, C₁₆-C₃₀aryl(arylalkyl)amido, thiol, C₁-C₃₀ hydroxyalkyl, C₆-C₁₄ hydroxyaryl,C₇-C₃₀ hydroxyarylalkyl, C₃-C₃₀ hydroxyalkenyl, C₃-C₃₀ hydroxyalkynyl,C₈-C₃₀ hydroxyarylalkenyl, C₈-C₃₀ hydroxyarylalkynyl, C₃-C₃₀ polyether,C₃-C₃₀ polyetherester, C₃-C₃₀ polyester, C₃-C₃₀ polyamino, C₃-C₃₀polyaminoamido, C₃-C₃₀ polyaminoether, C₃-C₃₀ polyaminoester, C₃-C₃₀polyamidoester, C₃-C₃₀alkylsulfonic acid, C₃-C₃₀alkylsulfonate salt,C₁-C₃₀ carboxylate salt, thiocarboxylate salt, dithiocarboxylate salt orC₃-C₃₀alkylC₁-C₄ trialkyammonium salt. Alkyl groups can be straight,branched, multiply branched, cyclic, or polycyclic where cyclic andpolycyclics can be unsubstituted, substituted, or polysubstituted,alkenyl can be a monoene, conjugated or non-conjugated polyene,straight, branched, multiply branched, cyclic, or polycyclic, terminalor internal, substituted at any carbon, E or Z isomers or mixturethereof, alkynes can be mono-yne, conjugated or non-conjugated poly-yne,terminal or internal, substituted at any carbon, aryl groups can becyclic, fused or unfused polycyclic of any geometry, asymmetricfunctional groups, such as ester and amido, can have either orientationwith respect to the alkylenedioxythiophene rings, poly can be 2 or more.Heteroatoms in substituents R¹-R⁸ can be at any position of thosesubstituents. For example an oxygen of an ether or ester or a nitrogenof an amine or amide can be in the alpha, beta, gamma or any otherposition relative to the point of attachment to the3,4-alkylenedioxythiophene. Heteroatom containing substituents can havea plurality of heteroatoms, for example, ether can be a monoether, adiether or a polyether, amine can be a monoamine, a diamine or apolyamine, ester can be a monoester, a diester, or a polyester, andamide can be a monoamide, a diamide or a polyamide. Ethers and estersgroups can be thioethers, thioesters and hydroxy groups can be thiol(mercapto) groups, where sulfur is substituted for oxygen. In oneembodiment of the invention, x is 1, y is 0, and R¹, R², R⁵ and R⁶ arehydrogen and R³=R⁴≠H. In one embodiment of the invention x is 1, y is 0,and R¹, R², R⁵ and R⁶ are hydrogen and R³=R⁴=CH₂OR where R is an alkylgroup. Salts can be those of alkali or alkali earth metals, ammoniumsalts, or phosphonium salts.

In other embodiments of the invention a yellow conjugated polymer has analternating sequence of first and second repeating units of thestructure:

where A is an aromatic unit, thiophene unit, furan unit, pyrrole unit,selenophene unit, or any combination thereof; n is 2 to 200,000; X is S,Se, O, or NR; where R, R⁹ and R¹⁰ are independently H, C₁-C₃₀ alkyl,C₂-C₃₀ alkenyl, C₂-C₃₀ alkynyl, C₆-C₁₄ aryl, C₇-C₃₀ arylalkyl, C₈-C₃₀arylalkenyl, C₈-C₃₀ arylalkynyl, C₂-C₃₀ alkylester, C₇-C₁₅ arylester,C₈-C₃₀ alkylarylester, C₃-C₃₀ alkenylester, C₃-C₃₀ alkynylester, NH₂,C₁-C₃₀ alkylamino, C₆-C₁₄ arylamino, C₇-C₃₀ (arylalkyl)amino, C₂-C₃₀alkenylamino, C₂-C₃₀ alkynylamino, C₈-C₃₀ (arylalkenyl)amino, C₈-C₃₀(arylalkynyl)amino, C₂-C₃₀ dialkylamino, C₁₂-C₂₈ diarylamino, C₄-C₃₀dialkenylamino, C₄-C₃₀ dialkynylamino, C₇-C₃₀ aryl(alkyl)amino, C₇-C₃₀di(arylalkyl)amino, C₈-C₃₀ alkyl(arylalkyl)amino, C₁₅-C₃₀aryl(arylalkyl)amino, C₈-C₃₀ alkenyl(aryl)amino, C₈-C₃₀alkynyl(aryl)amino, C(O)NH₂ (amido), C₂-C₃₀ alkylamido, C₇-C₁₄arylamido, C₈-C₃₀ (arylalkyl)amido, C₂-C₃₀ dialkylamido, C₁₂-C₂₈diarylamido, C₈-C₃₀ aryl(alkyl)amido, C₁₅-C₃₀ di(arylalkyl)amido, C₉-C₃₀alkyl(arylalkyl)amido, C₁₆-C₃₀ aryl(arylalkyl)amido, thiol, C₁-C₃₀alkylhydroxy, C₆-C₁₄ arylhydroxy, C₇-C₃₀ arylalkylhydroxy, C₃-C₃₀alkenylhydroxy, C₃-C₃₀ alkynylhydroxy, C₈-C₃₀ arylalkenylhydroxy, C₈-C₃₀arylalkynylhydroxy, C₃-C₃₀ polyether, C₃-C₃₀ polyetherester, C₃-C₃₀polyester C₃-C₃₀ polyamino, C₃-C₃₀ polyaminoamido, C₃-C₃₀polyaminoether, C₃-C₃₀ polyaminoester, C₃-C₃₀ polyamidoester,C₃-C₃₀alkylsulfonic acid, C₃-C₃₀alkylsulfonate salt, or C₃-C₃₀alkylC₁-C₄ trialkyammonium salt. Alkyl groups can be straight, branched,multiply branched, cyclic, or polycyclic where cyclic and polycyclicscan be unsubstituted, substituted, or polysubstituted, alkenyl can be amonoene, conjugated or non-conjugated polyene, straight, branched,multiply branched, cyclic, or polycyclic, terminal or internal,substituted at any carbon, E or Z isomers or mixture thereof, alkynescan be mono-yne, conjugated or non-conjugated poly-yne, terminal orinternal, substituted at any carbon, aryl groups can be cyclic, fused orunfused polycyclic of any geometry, asymmetric functional groups, suchas ester and amido, can have either orientation with respect to the3,4-dioxythiophene rings, poly can be 2 or more. Heteroatoms insubstituents R¹ and R² can be at any reasonable position of thosesubstituents. For example an oxygen of an ether or ester or a nitrogenof an amine or amide can be in the beta, gamma or any other positionrelative to the point of attachment to the 3,4-dioxythiophene, but notthe alpha position. Heteroatom containing substituents can have aplurality of heteroatoms, for example ether can be a monoether, adiether or a polyether, amine can be a monoamine, a diamine or apolyamine, ester can be a monoester, a diester, or a polyester, andamide can be a monoamide, a diamide or a polyamide. Ethers and estersgroups can be thioethers, thioesters and hydroxy groups can be thiol(mercapto) groups, where sulfur is substituted for oxygen. Salts can bethose of alkali or alkali earth metals, ammonium salts, or phosphoniumsalts.

In embodiments of the invention the yellow conjugated polymer sequenceis a portion of a block copolymer, graft copolymer, or polymer networkwhere non-conjugated polymer portion(s) can be any polymer that can beprepared by a step-growth or chain-growth process. For example, as canbe appreciated by one skilled in the art, a triblock copolymer can beformed where a non-coloring polymer mono-terminated with either or bothof the alternating units can be employed as end-capping monofunctionalunits in a condensation polymerization with a plurality of difunctionalmonomers for the yellow conjugated polymer's alternating sequencecontaining portion according to an embodiment of the invention. Inanother embodiment of the invention, a non-conjugated polymer can beterminated at both ends with one of either of the monomers for thealternating EC portion to form a multiblock polymer upon condensationwith the appropriate proportions of the two monomers for the yellowconjugated polymer portion. In another embodiment of the invention anon-conjugated polymer with substitution of one of the complementarymonomers of the conjugated polymer portion can be condensed with yellowconjugated polymer forming monomers to yield graft-like or networkcopolymers. The yellow conjugated polymer segments can be formed before,during or after the formation of the non-conjugated polymer portion ofblock copolymers, as can be appreciated by one skilled in the art.

In embodiments of the invention, the yellow conjugated polymer can betransformed into a different polymer, by reactions on the conjugatedpolymer portion. For example, but not limited to, the reaction can be atransformation of the substituents on one or more of the alternatingrepeating units. In some embodiments of the invention the yellowconjugated polymer can contain, for example, a reactive PropOT ofstructure, as shown in structure I above, where R¹ through R⁶ groupspermit processing of the yellow conjugated polymer into a film that canbe subsequently converted to a different yellow conjugated polymer and,for example, a soluble film can be converted into an insoluble film. Forexample, where R³ and R⁴ are di-ester groups, conversion to carboxylicacid groups can be carried out in the manner disclosed in Reynolds etal. U.S. Pat. No. 7,799,932, Sep. 21, 2010, and incorporated byreference herein. If desired, the di-acid can be subsequently convertedinto a carboxylate salt. Reactions can also involve one or more units ofthe other polymeric segments of block copolymers other than those of theconjugated polymer portion. Repeating units or terminal ends of theyellow conjugated polymer can be substituted to promote self associateor cross-associate with plurally functional additives to form asuper-molecular structure through non-covalent interactions such ashydrogen bonding, ion-dipole, ion pairing, ion chelation, dipole-dipole,or other non-covalent bonding forces. For example, some repeating unitsmay be substituted with specific polyol groups that are readily solvatedby a solvent, but strongly associate specifically with one or more otherpolyol groups of the yellow conjugated polymer or of an additive uponremoval of the solvent to form a super-molecular yellow conjugatedpolymer complex. In some embodiments of the invention, the polymerhaving a yellow conjugated polymer portion can be cross-linked, forexample after deposition on a surface that will be part of a device, forexample, an electrochromic device. For example, repeating units of thepolymer can have a functional group that can be induced to add to orcondense with another group upon activation or initiation that is withinthe conjugated polymer or on a reagent that is difunctional orpolyfunctional that is added to the yellow conjugated polymer. Forexample vinyl units can be induced to undergo vinyl addition, cyclicgroups can be induced to undergo ring-opening addition, or complementarygroups can undergo catalyzed addition or condensation to form a network.Functionalities that can be employed can be appreciated by those skilledin the art. For example, a precursor to a yellow conjugated polymernetwork can be deposited on a surface from solution and a catalyst, areagent, heat or radiation can be used to cause network formation. Inmany cases a precursor to a yellow conjugated polymer network is anon-network yellow conjugated polymer according to an embodiment of theinvention.

Other embodiments of the invention are directed to a method of preparingthe yellow conjugated polymer by cross-coupling reaction of anelectrophilic 3,4-alkylenedioxythiophene substituted on the alkylenebridge (I) or 3,4-dialkoxythiophene unit (II) and a nucleophilicaromatic donor unit by a Suzuki condensation; a specific example of thiscondensation is shown in FIG. 2. The present method allows sufficientmolecular weight where the fully conjugated limit of the pi to pi*transition is reached and the polymer can be solution processable as afilm yellow conjugated polymers because reliable purifications of thenucleophilic monomer and the electrophilic monomer can be effectivelycarried out. As with virtually all cross-coupling step-growthpolymerizations, the degree of polymerization for yellow conjugatedpolymers is limited by any deviation from stoichiometry. Hence thepurity of both monomers is critical to achieving a sufficiently largepolymer for use in many viable electrochromic devices. The electrophilicmonomers are substituted with leaving groups such as halogens,triflates, tosylates, mesylates, nosylates, trifluoroacetates or othersubstituted sulfonates that can act as the leaving group. In someembodiments of the invention the nucleophilic monomers can besubstituted with tin or zinc moieties rather than boron moieties asshown in FIG. 2. Coupling reactions that can be used for the preparationof the yellow conjugated polymers, include, but are not restricted to:Suzuki coupling, Stille coupling, Kumada coupling, Hiyama coupling,Negishi coupling, and Grignard methathesis (GRIM).

In embodiments of the invention the yellow conjugated polymer sequencecan have structure I, where x is 1 and y is 0, which is a substitutedpropylene bridge of, for example, a PropOT-A yellow conjugated polymerwhere variations in the composition permit the tuning of theelectrochromic features and permit a desired device fabrication method.In some embodiments of the invention the substituents comprise non-polarside chains. In other embodiments the substituents comprise polar orionic side chains, including but not exclusive to: ether, ester, amide,carboxylic acid, sulfonate, and amine functionalized chains. By theincorporation of polar or ionic substituents, the yellow conjugatedpolymers can be designed to adsorb on metal or metal oxide surfaces, forexample, but not limited to, titania for use in solar cells (GraetzelCells) or other devices. An electrochromic device can be formed by alayer-by-layer deposition process when a substituent that impartssolubility to the yellow conjugated polymer is included with one or moreother conjugated polymers that provide one or more different colors. Inan embodiment of the invention, an ED displays all colors by thesubtractive color mixing of Cyan Magenta Yellow (CMYK) or Red YellowBlue (RYB) conjugated polymers employing the yellow conjugated polymer,according to an embodiment of the invention. The desired colors can beachieved by: sequentially patterning the multiple colors (CMY or RYB) ina layered fashion to achieve color mixing; patterning in a lateralconfiguration, such that the patterned pixels are small enough and closeenough that the human eye sees the adjacent colors as a mixture; orstacking as films on separate electrodes to mix colors. For example, thepolymers of colors red, yellow, and blue can be patterned as clusters ofsquares, rectangles, circles, triangles, or other regular or irregularshapes, onto patterned electrode pixels to combine the colors at eachpixel and allow the resulting observed color to be any color of thevisible spectrum. For example, when the red and yellow polymers are intheir neutral state, and the blue polymer is in a colorless oxidizedstate, the pixel displays the color orange, and, when the yellow andblue pixels are in the neutral state with the red pixel in a colorlessoxidized state, the displayed color is green.

The yellow conjugated polymers according to embodiments of the inventioncan be employed in a wide variety of applications. For example, theyellow conjugated polymer can be a component of an active layer in bulkheterojunction solar cells. The R¹ and R² groups of the3,4-dialkoxythiophenes unit of polymer II can be of a structure thatdirects and enhances adsorption of the yellow conjugated polymer to ametal oxide through a polar carboxylate or even phosphatefunctionalities for use in dye sensitized solar cells, where the yellowEC polymer functions as the active light absorbing layer. Other uses forthe yellow conjugated polymers according to embodiments of the inventionare as charge transport layers and charge injection layers forfield-effect transistor devices.

Methods and Materials

Synthesis of a Yellow Conjugated Polymer (ECP Yellow-1)

A vial was charged with6,8-dibromo-3,3-bis(((2-ethylhexyl)oxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]di-oxepine(699.87 mg, 1.169 mmol) and transferred as a hexanes solution (10 mL)into a schlenk tube. After removal of the hexanes in vacuo, the tube wascharged with 1,4-benzene diboronic acid bis(pinecol) ester (387.7 mg,1.1748 mmol), K₃PO₄ (3.184 g, 0.015 mol), P(o-tol)₃ (20 mg, 0.06571mmol), Pd₂dba₃ (10.7 mg, 0.01169 mmol, 1 mol % Pd/Br), and one drop ofaliquat 336. The mixture was placed under vacuum for 2 hours. The tubewas backfilled with argon gas, and the vacuum-purge cycle was repeated 3times. Toluene (15 mL) and water (5 L) were added, and the mixture wasstirred at 85° C. for 3 days. After addition of4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane (550 mg, 2.7 mmol), themixture was stirred for 8 hours at 85° C., after which bromobenzene(0.37 mL, 3.5 mmol) was added and the mixture stirred overnight. Toluene(20 mL) was added, and the mixture was precipitated into a mixture ofmethanol (200 mL) and 1M HCl (25 mL). The precipitate was filtered intoa 25 mm×80 mm cellulose thimble, washed 3 times with methanol (30 mL)and again three times with DI water (30 mL). The precipitate waspurified by soxhlet extractions: methanol (one day), acetone (one day),hexanes (one day), and chloroform (one day). The chloroform solublefraction was treated with a spatula tip amount of diethylammoniumdithiocarbonate and stirred for 10 minutes and concentrated to about 50mL. The concentrated solution was pipetted dropwise into 200 mL of HPLCgrade methanol, and the resulting precipitate was filtered on a nylonfilter membrane. The polymer was then collected and dried in vacuo toyield a brown solid, which forms yellow films. Yield 83% (530 mg). GPCM_(w)=42,230, M_(n)=24,968, PDI=1.69. ¹H NMR (CDCl₃): δ 7.78 (br s, 4H),4.2 (br s, 4H), 3.58 (br s, 4H), 3.36 (br s, 4H), 1.6-1.2 (br, 20H),0.96 (br s, 14H) Anal. calcd. for C₃₈H₅₄O₄S C, 72.33; H, 9.01. Found C,72.47; H, 9.81.

Synthesis of a yellow Conjugated Polymer (ECP Yellow-2)

A vial was charged with6,8-dibromo-3,3-bis(((2-ethylhexyl)oxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]di-oxepine(700 mg, 1.169 mmol) and transferred as a hexanes solution (10 mL) intoa schlenk tube. After removal of the hexanes in vacuo, the tube wascharged with 9,9-dioctylfluorene 2,7-bis-diboronic acid bis(pinecol)ester (755.34 mg, 1.1755 mmol), K₃PO₄ (3.184 g, 0.015 mol), P(o-tol)₃(20 mg, 0.06571 mmol), Pd₂ dba₃ (10 mg, 0.01169 mmol, 1 mol % Pd/Br),and two drops of aliquat 336. The mixture was placed under vacuum for 2hours. The tube was backfilled with argon gas, and the vacuum-purgecycle was repeated 3 times. Toluene (15 mL) and water (5 mL) were added,and the mixture was stirred at 90° C. for 3 days. After addition of4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane (550 mg, 2.7 mmol), themixture was stirred for 8 hours at 85° C., after which, bromobenzene(0.37 mL, 3.5 mmol) was added and the mixture stirred overnight. Toluene(20 mL) was added, and the mixture was precipitated into a mixture ofmethanol (200 mL) and 1M HCl (25 mL). The precipitate was filtered intoa 25 mm×80 mm cellulose thimble, washed 3 times with methanol (30 mL)and three times with DI water (30 mL). The precipitate was purified bysoxhlet extractions: methanol (one day), acetone (one day), hexanes (oneday), and chloroform (one day). The chloroform soluble fraction wastreated with a spatula tip amount of diethylammonium dithiocarbonate andstirred for 10 minutes and concentrated to about 50 mL. The concentratedsolution was pipetted dropwise into 200 mL of HPLC grade methanol, andthe resulting precipitate was filtered on a nylon filter membrane. Thepolymer was then collected and dried in vacuo to yield a yellow-greensolid, which forms yellow films. Yield 80% (773 mg). GPC M_(w)=17,653,M_(n)=12,008, PDI=1.47. ¹H NMR (CDCl₃): δ 7.8 (br s, 2H), 7.7 (br s,4H), 4.2 (br s, 4H), 3.58 (br s, 4H), 3.36 (br s, 4H), 2.1 (br s, 4H),1.6-1.2 (br, 20H), 0.96 (br s, 14H) Anal. calcd. for C₅₄H₈₂O₄S C, 78.40;H, 9.99. Found C, 78.79; H, 10.221.

Yellow Conjugated Polymer (ECP Yellow-1) Characterization

The yellow conjugated polymer was spray-cast onto ITO coated glassslides from a ˜2 mg/mL toluene solution. Electrochemical switching bycyclic voltammetry (50 mV/s, 0.2 M lithiumbistrifluoromethanesuflonamide (LiBTI)/propylene carbonate solution)between 180 mV and 1080 mV vs. Fc/Fc⁺ was carried out until a stable andreproducible voltammogram was observed and spectroelectrochemicalanalysis was obtained. FIG. 3 shows the spectroelectrochemical responsein absorbance (left) and percent transmittance (right). As can be seenin the absorbance spectrum in FIG. 3 (left), a sharp absorption bandwith λ_(max) at 455 nm is present in the neutral state. The onset ofabsorption reveals a bandgap of around 2.38 eV. Upon oxidation, theintensity of absorption at 455 nm is significantly reduced, while apolaronic transition arises around 650 nm. The intensity of thepolaronic transition depletes at higher oxidation levels, giving way tobipolaronic absorption with λ_(max) greater than 1600 nm. As illustratedin the transmittance spectrum, FIG. 3 (right), the fully oxidizedpolymer is more than 75% transmissive across the entire visible range(400-750 nm).

To evaluate the color of the polymer films as perceived by the humaneye, L*a*b* values for three polymer films were measured as a functionof the electrochemical doping level, and a* b* values for each step (50mV, 180 to 1080 mV vs Fc/Fc⁺) are plotted in FIG. 4. Photographs of eachfilm in the neutral and fully oxidized states corroborate the accuracyof the L*a*b* values. Extremely high b* values in the neutral stateindicate that the material is a saturated yellow as viewed by the humaneye, and is evident in photographs. The films also display smallnegative a* values indicative of a green hue, possibly due to ayellow-green emission from the polymer films. As oxidation progresses, asmall negative b* value indicates that a faint blue intermediate stateoccurs just before doping is complete. At around 1040 mV, only a smallnegative b* value remains and a* values are near zero, as the highlytransmissive film has a faint sky blue color.

The yellow conjugated polymer's utility for use in display type devicesis indicated by the speed at which the polymer can be switched from onecolor state to another, as rapidly switching materials are required.FIG. 5 shows the change in absorbance at the λ_(max) of a spray-castfilm as a function of time as potential square waves were applied. Ascan be seen by FIG. 5, the film exhibits an excellent contrast, 73%, at455 nm, and is able to retain almost all of that contrast at switchingrates as high as 1 second per potential step. Even at a rate of 0.5seconds per potential, the polymer retains 63% contrast. Potentially, byoptimizing the solvent/electrolyte/conjugated polymer mixture, switchingwith up to 95% of contrast for a full switching rate of less than 250milliseconds is envisioned.

To evaluate the yellow conjugated polymer for use in anelectroluminescent device, a polymer light emitting diode was fabricatedusing a sandwich configuration of ITO/PEDOT:PSS/Yellow conjugatedpolymer/LiF/Al. FIG. 6 shows the electroluminescence spectrum of theyellow conjugated polymer based device at an applied current density of300 mA/cm². As can be seen in FIG. 6, when incorporated in anelectroluminescent device, the yellow polymer emits light with a maximumwavelength of around 550 nm with tailing to longer wavelengths,observable as a yellow-green color to the eye, which indicates thatyellow conjugated polymers according to embodiments of the invention canbe used for fabrication of dual electrochromic/electroluminescentdevices.

FIG. 7 shows shadow mask deposited on thin transparent films, whereoverlapping films of yellow conjugated polymer, blue conjugated polymer,and red conjugated polymer generate a Venn diagram by the positioning ofthe thin films. Combinations of such films allow a full color display,where the intensity of each of the three primaries can be controlled togenerate any desired color. FIG. 7 (top) shows yellow and blue filmsoverlapping to generate green, yellow and red films overlapping togenerate orange, and red and blue films overlapping to generate purple.Where all of the colored films overlap, black is observed. FIG. 7(bottom) shows these overlapping films in a neutral colored state (left)and these overlapping films in an oxidized transmissive state (right).

Yellow Conjugated Polymer (ECP Yellow-2) Characterization

The yellow conjugated polymer was spray-cast onto ITO coated glassslides from a ˜3 mg/mL toluene solution. Electrochemical switching bycyclic voltammetry (50 mV/s, 0.2 M lithiumbistrifluoromethanesuflonamide (LiBTI)/propylene carbonate solution)between 480 mV and 960 mV vs. Fc/Fc⁺ was carried out until a stable andreproducible voltammogram was observed, whereupon spectroelectrochemicalanalysis was obtained. FIG. 8 shows the spectroelectrochemical responsein absorbance (top) and percent transmittance (bottom). As can be seenin the absorbance spectrum in FIG. 8 (top), a sharp absorption band withλ_(max) at 434 nm is present in the neutral state. The onset ofabsorption reveals a bandgap of around 2.44 eV. Upon oxidation, theintensity of absorption at 434 nm is significantly reduced, while apolaronic transition arises around 628 nm, which blue-shifts to 526 nmover the period of oxidation. The intensity of the polaronic transitiondecreases at higher oxidation levels, giving way to bipolaronicabsorption with a λ_(max) greater than 1600 nm. As illustrated in thetransmittance spectrum, FIG. 8 (bottom), the fully oxidized polymerexhibits ˜60% transmission across the entire visible range (400-750 nm).

T color of the ECP Yellow-2 polymer films, as perceived by the humaneye, were assigned L*a*b* values for the average of three polymer filmsat different electrochemical doping levels. The a* b* values determinedfor each step of 50 mV over the range of 480 to 960 mV vs Fc/Fc⁺), asplotted in FIG. 9. Photographs of each film in the neutral and fullyoxidized states corroborate the accuracy of the L*a*b* values. High b*values in the neutral state indicate that the material is a saturatedyellow as viewed by the human eye, and is evident in photographs. Thefilms also display small negative a* values, indicative of a green hue,possibly due to a yellow-green emission from the polymer films. Asoxidation progresses, a small negative b* value indicates that a faintblue intermediate state occurs just before doping is complete. At around850 mV, only a small negative b* value remains and a* values are nearzero, as the highly transmissive film has a faint sky blue color.Continuing the oxidation to 1050 mV, the films begin to exhibit a pinkhue.

The yellow conjugated polymer's utility for display type devices isindicated by the speed at which the polymer can be switched from onecolor state to another, as rapidly switching materials are required.FIG. 10 shows the change in absorbance at λ_(max) for a spray-cast film,as a function of time when potential square waves were applied. As canbe seen by FIG. 10, the film exhibits an excellent contrast, 59.4% at434 nm, which can be retained at switching rates as high as 2 second perpotential step.

All patents, patent applications, provisional applications, andpublications referred to or cited herein are incorporated by referencein their entirety, including all figures and tables, to the extent theyare not inconsistent with the explicit teachings of this specification.

It should be understood that the examples and embodiments describedherein are for illustrative purposes only and that various modificationsor changes in light thereof will be suggested to persons skilled in theart and are to be included within the spirit and purview of thisapplication.

1. A conjugated polymer, comprising a fully conjugated polymericsequence of at least two alternating triads comprising: a firstrepeating unit selected from dioxythiophene, dioxyfuran, dioxypyrrole,dioxyselenophene, or any combination thereof; and a second repeatingunit selected from an aromatic molecule, thiophene, furan, pyrrole,selenophene, or any combination thereof, wherein the conjugated polymeris yellow in its neutral state and having an absorption maximum between300 and 500 nm that upon oxidation is transmissive between 400-750 nm.2. The conjugated polymer of claim 1, wherein the conjugated polymericsequence has the structure:

where A is an aromatic unit, thiophene unit, furan unit, pyrrole unit,selenophene unit, or any combination thereof; n is 2 to 200,000; X is S,Se, O, or NR; R, R⁹, and R¹⁰ are independently H, C₁-C₃₀ alkyl, C₂-C₃₀alkenyl, C₂-C₃₀ alkynyl, C₆-C₁₄ aryl, C₇-C₃₀ arylalkyl, C₈-C₃₀arylalkenyl, C₈-C₃₀ arylalkynyl, C₂-C₃₀ alkylester, C₇-C₁₅ arylester,C₈-C₃₀ alkylarylester, C₃-C₃₀ alkenylester, C₃-C₃₀ alkynylester, NH₂,C₁-C₃₀ alkylamino, C₆-C₁₄ arylamino, C₇-C₃₀ (arylalkyl)amino, C₂-C₃₀alkenylamino, C₂-C₃₀ alkynylamino, C₈-C₃₀ (arylalkenyl)amino, C₈-C₃₀(arylalkynyl)amino, C₂-C₃₀ dialkylamino, C₁₂-C₂₈ diarylamino, C₄-C₃₀dialkenylamino, C₄-C₃₀ dialkynylamino, C₇-C₃₀ aryl(alkyl)amino, C₇-C₃₀di(arylalkyl)amino, C₈-C₃₀ alkyl(arylalkyl)amino, C₁₅-C₃₀aryl(arylalkyl)amino, C₈-C₃₀ alkenyl(aryl)amino, C₈-C₃₀alkynyl(aryl)amino C(O)NH₂ (amido), C₂-C₃₀ alkylamido, C₇-C₁₄ arylamido,C₈-C₃₀ (arylalkyl)amido, C₂-C₃₀ dialkylamido, C₁₂-C₂₈ diarylamido,C₈-C₃₀ aryl(alkyl)amido, C₁₅-C₃₀ di(arylalkyl)amido, C₉-C₃₀alkyl(arylalkyl)amido, C₁₆-C₃₀ aryl(arylalkyl)amido, thiol, C₁-C₃₀alkylhydroxy, C₆-C₁₄ arylhydroxy, C₇-C₃₀ arylalkylhydroxy, C₃-C₃₀alkenylhydroxy, C₃-C₃₀ alkynylhydroxy, C₈-C₃₀ arylalkenylhydroxy, C₈-C₃₀arylalkynylhydroxy, C₃-C₃₀ polyether, C₃-C₃₀ polyetherester, C₃-C₃₀polyester C₃-C₃₀ polyamino, C₃-C₃₀ polyaminoamido, C₃-C₃₀polyaminoether, C₃-C₃₀ polyaminoester, C₃-C₃₀ polyamidoester, C₃-C₃₀alkylsulfonic acid, C₃-C₃₀ alkylsulfonate salt, C₁-C₃₀ carboxylate salt,C₁-C₃₀ thiocarboxylate salt, C₁-C₃₀ dithiocarboxylate salt, or C₃-C₃₀alkyl C₁-C₄ trialkyammonium salt; and R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸are independently H, C₁-C₃₀ alkyl, C₂-C₃₀ alkenyl, C₂-C₃₀ alkynyl,C₆-C₁₄ aryl, C₇-C₃₀ arylalkyl, C₈-C₃₀ arylalkenyl, C₉-C₃₀ arylalkynyl,hydroxy, C₁-C₃₀ alkoxy, C₆-C₁₄ aryloxy, C₇-C₃₀ arylalkyloxy, C₂-C₃₀alkenyloxy, C₂-C₃₀ alkynyloxy, C₈-C₃₀ arylalkenyloxy, C₈-C₃₀arylalkynyloxy, CO₂H, C₂-C₃₀ alkylester, C₇-C₁₅ arylester, C₈-C₃₀alkylarylester, C₃-C₃₀ alkenylester, C₃-C₃₀ alkynylester, NH₂, C₁-C₃₀alkylamino, C₆-C₁₄ arylamino, C₇-C₃₀ (arylalkyl)amino, C₂-C₃₀alkenylamino, C₂-C₃₀ alkynylamino, C₈-C₃₀ (arylalkenyl)amino, C₈-C₃₀(arylalkynyl)amino, C₂-C₃₀ dialkylamino, C₁₂-C₂₈ diarylamino, C₄-C₃₀dialkenylamino, C₄-C₃₀ dialkynylamino, C₇-C₃₀ aryl(alkyl)amino, C₇-C₃₀di(arylalkyl)amino, C₈-C₃₀ alkyl(arylalkyl)amino, C₁₅-C₃₀aryl(arylalkyl)amino, C₈-C₃₀ alkenyl(aryl)amino, C₉-C₃₀alkynyl(aryl)amino, C(O)NH₂ (amido), C₂-C₃₀ alkylamido, C₇-C₁₄arylamido, C₈-C₃₀ (arylalkyl)amido, C₂-C₃₀ dialkylamido, C₁₂-C₂₈diarylamido, C₈-C₃₀ aryl(alkyl)amido, C₁₅-C₃₀ di(arylalkyl)amido, C₉-C₃₀alkyl(arylalkyl)amido, C₁₆-C₃₀ aryl(arylalkyl)amido, thiol, C₁-C₃₀hydroxyalkyl, C₆-C₁₄ hydroxyaryl, C₇-C₃₀ hydroxyarylalkyl, C₃-C₃₀hydroxyalkenyl, C₃-C₃₀ hydroxyalkynyl, C₈-C₃₀ hydroxyarylalkenyl, C₈-C₃₀hydroxyarylalkynyl, C₃-C₃₀ polyether, C₃-C₃₀ polyetherester, C₃-C₃₀polyester, C₃-C₃₀ polyamino, C₃-C₃₀ polyaminoamido, C₃-C₃₀polyaminoether, C₃-C₃₀ polyaminoester, C₃-C₃₀ polyamidoester, C₃-C₃₀alkylsulfonic acid, C₃-C₃₀ alkylsulfonate salt, C₁-C₃₀ carboxylate salt,C₁-C₃₀ thiocarboxylate salt, C₁-C₃₀ dithiocarboxylate salt or C₃-C₃₀alkylC₁-C₄ trialkyammonium salt.
 3. The conjugated polymer of claim 1,wherein the aromatic unit, thiophene unit, furan unit, pyrrole unitcomprises:

where: X is NR′, PR′, S, O, Se, SO_(x), CR₂, SiR′₂, GeR′₂, or BR′, wherex=1 or 2; X′ is NR′, O, Se, or S; where R′ is H, C₁-C₃₀ alkyl, C₂-C₃₀alkenyl, C₂-C₃₀ alkynyl, C₆-C₁₄ aryl, C₇-C₃₀ arylalkyl, C₈-C₃₀arylalkenyl, C₈-C₃₀ arylalkynyl, C₁-C₃₀ hydroxyalkyl, C₆-C₁₄hydroxyaryl, C₇-C₃₀ hydroxyarylalkyl, C₃-C₃₀ hydroxyalkenyl, C₃-C₃₀hydroxyalkynyl, C₈-C₃₀ hydroxyarylalkenyl, C₈-C₃₀ hydroxyarylalkynyl,C₃-C₃₀ polyether, C₃-C₃₀ polyetherester, C₃-C₃₀ polyester, C₃-C₃₀polyamino, C₃-C₃₀ polyaminoamido, C₃-C₃₀ polyaminoether, C₃-C₃₀polyaminoester, C₃-C₃₀ polyamidoester, C₃-C₃₀alkylsulfonic acid,C₃-C₃₀alkylsulfonate salt, C₁-C₃₀ alkylcarboxylate salt, C₁-C₃₀alkylthiocarboxylate salt, C₁-C₃₀ alkyldithiocarboxylate salt or C₃-C₃₀alkyl C₁-C₄ trialkyammonium salt; R″ is independently H, C₁-C₃₀ alkyl,C₃-C₃₀ alkenyl, C₂-C₃₀ alkynyl, C₅-C₁₄ aryl, C₇-C₃₀ arylalkyl, C₈-C₃₀arylalkenyl, C₈-C₃₀ arylalkynyl; and R is independently H, C₁-C₃₀ alkyl,C₂-C₃₀ alkenyl, C₂-C₃₀ alkynyl, C₆-C₁₄ aryl, C₇-C₃₀ arylalkyl, C₈-C₃₀arylalkenyl, C₈-C₃₀ arylalkynyl, hydroxy, C₁-C₃₀ alkoxy, C₆-C₁₄ aryloxy,C₇-C₃₀ arylalkyloxy, C₂-C₃₀ alkenyloxy, C₂-C₃₀ alkynyloxy, C₈-C₃₀arylalkenyloxy, C₈-C₃₀ arylalkynyloxy, CO₂H, C₂-C₃₀ alkylester, C₇-C₁₅arylester, C₈-C₃₀ alkylarylester, C₃-C₃₀ alkenylester, C₃-C₃₀alkynylester, NH₂, C₁-C₃₀ alkylamino, C₆-C₁₄ arylamino, C₇-C₃₀(arylalkyl)amino, C₂-C₃₀ alkenylamino, C₂-C₃₀ alkynylamino, C₈-C₃₀(arylalkenyl)amino, C₈-C₃₀ (arylalkynyl)amino, C₂-C₃₀ dialkylamino,C₁₂-C₂₈ diarylamino, C₄-C₃₀ dialkenylamino, C₄-C₃₀ dialkynylamino,C₇-C₃₀ aryl(alkyl)amino, C₇-C₃₀ di(arylalkyl)amino, C₈-C₃₀alkyl(arylalkyl)amino, C₁₅-C₃₀ aryl(arylalkyl)amino, C₈-C₃₀alkenyl(aryl)amino, C₈-C₃₀ alkynyl(aryl)amino C(O)NH₂ (amido), C₂-C₃₀alkylamido, C₇-C₁₄ arylamido, C₈-C₃₀ (arylalkyl)amido, C₂-C₃₀dialkylamido, C₁₂-C₂₈ diarylamido, C₈-C₃₀ aryl(alkyl)amido, C₁₅-C₃₀di(arylalkyl)amido, C₉-C₃₀ alkyl(arylalkyl)amido, C₁₆-C₃₀aryl(arylalkyl)amido, thiol, C₁-C₃₀ hydroxyalkyl, C₆-C₁₄ hydroxyaryl,C₇-C₃₀ hydroxyarylalkyl, C₃-C₃₀ hydroxyalkenyl, C₃-C₃₀ hydroxyalkynyl,C₈-C₃₀ hydroxyarylalkenyl, C₈-C₃₀ hydroxyarylalkynyl, C₃-C₃₀ polyether,C₃-C₃₀ polyetherester, C₃-C₃₀ polyester, C₃-C₃₀ polyamino, C₃-C₃₀polyaminoamido, C₃-C₃₀ polyaminoether, C₃-C₃₀ polyaminoester, C₃-C₃₀polyamidoester, C₃-C₃₀ alkylsulfonic acid, C₃-C₃₀alkylsulfonate salt,C₁-C₃₀ carboxylate salt, C₁-C₃₀ thiocarboxylate salt, C₁-C₃₀dithiocarboxylate salt, or C₃-C₃₀ alkylC₁-C₄ trialkyammonium salt. 4.The conjugated polymer of claim 1, wherein the fully conjugatedpolymeric sequence is an alternating copolymer or a portion of a randomcopolymer.
 5. The conjugated polymer of claim 1, wherein the fullyconjugated polymeric sequence is a portion of a block, graft, branched,hyperbranched, or dendritic copolymer.
 6. The conjugated polymer ofclaim 1, wherein the fully conjugated polymeric sequence is a portion ofa network.
 7. The conjugated polymer of claim 1, wherein the conjugatedpolymer or a polymeric precursor of the conjugated polymer is soluble inat least one solvent.
 8. The conjugated polymer of claim 7, wherein thesolvent comprises toluene, chloroform, dichloromethane, hexanes,tetrahydrofuran, chlorobenzene, water, ethanol, or other solvent.
 9. Theconjugated polymer of claim 1, wherein a thin film comprising theconjugated polymer in the neutral state displays a transmittance of lessthan about 40% between 400 nm and 500 nm and greater than about 90%transmittance from 600 nm-750 nm.
 10. The conjugated polymer of claim 1,wherein a thin film comprising the conjugated polymer in the oxidizedstate displays a transmittance of more than about 70% between 400 and750 nm.
 11. The conjugated polymer of claim 1, wherein the conjugatedpolymer is electrochromic or electroluminescent.
 12. A method for thepreparation of the conjugated polymer of claim 1, comprising: combiningin one or more solvents a plurality of one or more nucleophilicmonomeric aromatic units, thiophene units, furan units, pyrrole units,selenophene units or combination thereof that are disubstituted withgroups comprising tin, boron, zinc, and a plurality of one or moreelectrophilic monomeric dioxyhetereocyclic units having a pair ofleaving groups; or combining in one or more solvents a plurality of oneor more nucleophilic monomeric dioxyheterocyclic units that aredisubstituted with groups comprising tin, boron, zinc, silicon, ormagnesium and a plurality of one or more electrophilic monomericaromatic units, thiophene units, furan units, pyrrole units, selenopheneunits, or combination thereof having a pair of leaving groups;optionally adding a catalyst; and cross-coupling the nucleophilicmonomeric units with the electrophilic monomeric units to yield theconjugated polymer or a precursor of the conjugated polymer.
 13. Themethod of claim 12, wherein the conjugated polymer is soluble in atleast one solvent.
 14. The method of claim 12, wherein the leaving groupcomprises halogen, triflate, tosylate, nosylate, trifluoroacetate, ormesylate.
 15. The method of claim 12, wherein the halogen comprisesbromine.
 16. The method of claim 12, wherein the catalyst comprises apalladium or nickel comprising compound.
 17. The method of claim 12,wherein said cross-coupling comprises a Stille coupling, Kumadacoupling, Hiyama coupling, Negishi coupling, inverse Suzuki coupling, orGrignard methathesis (GRIM).
 18. An electrochromic device (ED),comprising the conjugated polymer of claim 1 and at least one non-yellowconjugated polymer that displays a primary subtractive color in aneutral state and is transmissive in an oxidized state.
 19. The ED ofclaim 18, wherein a plurality of the non-yellow conjugated polymersdisplay red and blue in the neutral state.
 20. The ED of claim 18,wherein a plurality of the non-yellow conjugated polymers displaymagenta and cyan in the neutral state.
 21. The ED of claim 18, whereinthe device is transmissive or reflective.
 22. A method of preparing anED comprising the conjugated polymer of claim 1, comprising depositionof the conjugated polymer from solution onto a surface.
 23. The methodof claim 22, wherein deposition comprises spraying, printing, slot diecoating, roll-to-roll coating, or electrostatic adsorption.